CN110494465A - Method for in-mould coating polymeric substrate - Google Patents
Method for in-mould coating polymeric substrate Download PDFInfo
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- CN110494465A CN110494465A CN201780089411.4A CN201780089411A CN110494465A CN 110494465 A CN110494465 A CN 110494465A CN 201780089411 A CN201780089411 A CN 201780089411A CN 110494465 A CN110494465 A CN 110494465A
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- Prior art keywords
- coating composition
- cavity
- coating
- basis material
- substrate
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C2037/0035—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied as liquid, gel, paste or the like
Abstract
Method for in-mould coating polymeric substrate comprising plastic basis material is introduced into the membrane cavity of mold；Coating composition is introduced into the die cavity containing the plastic basis material to coat the substrate under 50 °C -120 °C of processing temperature and 11,000 to 20,700 kPa of tonnage；Solidify with the composition made in the die cavity under 62 °C -105 °C of solidification temperature；Wherein the coating composition includes polymer and polyisocyanates containing isocyanate-reactive group, and wherein viscosity of the coating composition under the processing temperature is 200 to 500 mPas.Other embodiments include that electronic circuit, light emitting diode and/or graph image are attached on the plastic basis material, are then coated with.
Description
Field
The present invention relates to for in-mould coating polymeric substrate, particularly with electronic circuit attached thereto, shine
The method of the polymeric substrate of the figure or image of diode or sensitivity.
Background information
Two component polyurethane molding coating composition is widely used because of many favorable properties that they show.This
A little coating compositions generally comprise liquid binder component and liquid hardening agent/crosslinker component.Liquid binder component can wrap
Containing isocyanate-reactive component such as polyalcohol, and liquid cross-linker component may include polyisocyanates.Polyisocyanates
Addition reaction (it can occur at ambient conditions) with isocyanate-reactive component generates the crosslinking for forming coated film
Polyurethane network.Polyurethane coating is widely used, and one of which is commonly known as " in mould " coating.
In in-mould coating application, coated film is moulded on the surface of the plastic basis material of molding.In in-mould coating method
In, the plastic components of molding is introduced into cavity body of mould, injects coated film thereto.The mold can also be Multicarity metal
Mold then moves in the second cavity of the mold wherein the plastic components moulded is formed in a cavity of mold.This
Class method can have the advantage that compared to single-chamber body in-mould coating method.For example, cycle time is shorter, because it is not by each side
The temporal summation of method step forms, and technological parameter can be selected independently to each cavity.
However, it is possible to also need to add add-on assemble, such as electronic circuit, light emitting diode on the plastic base of molding
And sensitive figure or other images, such as bar code or QR code.Mould with this kind of electronic device, LED or sensitive figure
There are problems for interior coating method, because conventional coating method may move or damage these additional components, so that they can
It can not function as anticipated.Adding in mould in method with the liquid composition for forming effective coating is usually with high viscosity
Polymer, add at high temperature and pressure.These properties and condition can lead to coating composition movement or may damage electricity
Sub-circuit and LED.For graph image such as bar code or QR code, they can similarly be moved or via ink or its
Its colouring component is mobile or sprawls to cover the image and causes to be difficult to recognize in other ways.Simultaneously, it is necessary to existence condition
Coating to be fully introduced into mold to and be made its solidification, to allow to be effective as coating over the whole substrate and wrap
Seal sensitive electronic device and figure.
Therefore, it would be desirable to provide the method for in-mould coating, utilizes and coating composition is effectively introduced into mold
And the method for solidifying it without damaging this kind of electronic device or figure on substrate and sensitive additive.Make in view of the foregoing
The present invention is gone out.
Summary of the invention
It in one embodiment of the invention, include: that plastic basis material is introduced mold by (a) for the method for in-mould coating
Membrane cavity in；(b) (i) at 50 DEG C -120 DEG C of processing temperature, (ii) is under tonnage 11,000 to 20,700kPa by coating
Composition is introduced into the die cavity containing the plastic basis material to coat the substrate；(c) under 62-105 DEG C of solidification temperature
Solidify the composition in the die cavity；Wherein the coating composition include polymer containing isocyanate-reactive group and
Polyisocyanates, and wherein viscosity of the coating composition under the processing temperature is 200 to 500mPas.
In another embodiment, the plastic basis material includes aromatic polycarbonate.In another embodiment, electronics electricity
At least one of road, light emitting diode and graph image are attached on the plastic basis material.
In embodiments of the invention, the processing temperature can be 50-80 DEG C, and it is in another embodiment
66-77℃.In a different embodiment, the tonnage is 12,400 to 15,200kPa.In also another implementation
In scheme, the mold temperature is 71 DEG C to 82 DEG C.
There are also in another embodiment, the method can further comprise by the resin containing isocyanate-reactive
Polymer and the polyisocyanates are mixed into the step in mixing head, wherein component is mixed before being injected into the die cavity
It closes.In a different embodiment, the polymer and the polyisocyanates of the resin containing isocyanate-reactive it
One is fed in impact type mixing head via the aperture that diameter is 0.15mm-0.70mm.
In a not yet disclosed embodiment, the polymer containing isocyanate-reactive group includes: (i) virtue
Race's branched polyester polyalcohol；(ii) aliphatic polycarbonate polyalcohol.In another embodiment, the aliphatic polycarbonate is more
First alcohol is polycarbonate glycol.There are also in another embodiment, the polyisocyanates includes hexamethylene diisocyanate
Isocyanuric acid ester.
In a different embodiment, the coating composition with a thickness of 0.05mm to 3.5mm, preferably 0.5mm-
3.0mm.In another embodiment, coating surface substantially constant at a distance from the substrate.In still another embodiment, institute
It states coating composition and further includes plasticizer.
In an individual embodiment, this method further includes molded plastic substrate.In another embodiment, institute
Stating mold includes the first cavity and the second cavity, the plastic basis material is moulded in first cavity and by the coating group
Object is closed to be introduced into second cavity.
There are also in another embodiment, the method further includes addition comprising electronic circuit, light emitting diode and/
Or the film of graph image.In a different embodiment, the film is applied to and moulds the plastics base wherein
In the cavity of material.There are also in another embodiment, the method further includes by electronic circuit, light emitting diode and/or
Graph image is added on the plastic basis material, then introduces the coating composition.
Detailed description
" polymer " used herein covers prepolymer, oligomer and both homopolymer and copolymer；Herein
Prefix " more (poly) " refer to two or more.Unless otherwise specified, " molecular weight " used herein is when for polymerization
Object using when be number average molecular (" Mn").The M of polymer containing functional group such as polyalcohol used hereinnIt can be with
Calculated by number of functional groups such as hydroxyl value (it is determined by end-group analysis), as known to those skilled in the art that
Sample.
Term " aliphatic series " used herein refers to it is characterized in that the substituted or unsubstituted straight chain of carbon constituting atom, branch
The organic compound of change and/or closed chain arrangement.Aliphatic compounds are free of part of the aromatic ring as its molecular structure.Institute herein
Term " alicyclic " refers to the organic compound it is characterized in that arrangement of the carbon atom in closed loop configuration.Alicyclic chemical combination
Object is free of part of the aromatic ring as its molecular structure.Therefore, alicyclic compound is the subset of aliphatic compounds.Therefore, term
" aliphatic series " covers aliphatic compounds and/or alicyclic compound.
" diisocyanate " used herein refers to containing there are two the compounds of isocyanate groups.It is used herein
" polyisocyanates " refers to the compound containing two or more isocyanate groups.Therefore, diisocyanate is polyisocyanate cyanogen
The subset of acid esters.
As previously mentioned, some embodiments of the invention are related to the method for in-mould coating.Such methods include: (a)
Plastic basis material is introduced into membrane cavity；(b) coating composition is introduced into the die cavity containing the plastic basis material to coat the base
Material, (i) coating composition includes polymer and polyisocyanates containing isocyanate-reactive group, and (ii) is in temperature 50
At DEG C -120 DEG C, (iii) is at pressure 1600-3000psi (11,000 to 20,700kPa)；(c) in 62-105 DEG C of mold temperature
Degree and at least 100kg/mm2Make under the condition of cure of outer mold pressure the composition in the second die cavity solidify at least 60 seconds when
Between.In addition, as described above, the plastic basis material can have sensitive electrical devices attached thereto, for example, electronic circuit and/
Or LED.The substrate alternatively or additionally has graph image attached thereto, such as one or more bar codes
Or QR code.
The substrate can be for example, by injection moulding, injection compression molding, compression forming, reaction injection molding (RIM)
Or foaming generates in die cavity.Thermoplasticity and thermosetting plastics may be used as substrate material, and specific example includes but is not limited to
Polycarbonate (PC), polyester such as polybutylene terephthalate (PBT) (PBT) or polyethylene terephthalate (PET) gather
Amide (PA), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS),
Acrylonitrile-styrene-acrylic ester copolymer (ASA), poly- (styrene-acrylonitrile) (SAN), polyformaldehyde (POM), cyclic polyolefin
Hydrocarbon (COC), polyphenylene oxide (PPO), polymethyl methacrylate (PMMA), polyphenylene sulfide (PPS), polyurethane (PUR), epoxy resin
(EP), polyvinyl chloride (PVC) and its blend.Preferred substrate material is aromatic polycarbonate.The substrate, which can have, to be set
The standby any required shape that can be accommodated.
In certain embodiments, molding of the substrate in the first die cavity passes through injection moulding work by thermoplastic material
Skill carries out.Suitable thermoplastic material include but is not limited to PC, PBT, PA, PE, PP, PS, ABS, ASA, SAN, PET, POM,
COC, PPO/PA or PPO/PS blend, PMMA, PPS, thermoplastic polyurethane (TPU), EP, PVC and its blend.
In some embodiments of the present invention, the compound that is molded in such as silicone of the substrate in the first die cavity
In the presence of carry out, the compound have isocyanate-reactive functional group, such as mercaptan, amine and/or hydroxyl group.Therefore,
Such compound may be constructed the part of the substrate itself, and due to it include can in the coating composition that then applies
Isocyanate groups reaction group.As a result, it is now recognized that its substrate that can improve molding is to the adhesiveness of coating.If
The compound is silicone, then silicone can serve as the release agent for promoting the substrate of molding to be detached from from the first die cavity.Suitable for this
The example of this kind of compound in invention includes but is not limited to the poly- (dimethyl siloxane) and poly- of bis- (3- aminopropyls) sealing end
Caprolactone-is poly- (dimethyl siloxane).
Add-on assemble such as electronic circuit, light emitting diode (LED) or figure such as bar code and QR code can be adhered to
On the substrate.The form of film that this kind of add-on assemble can be applied in mold is added on the substrate, so that should
Substrate is formed around the mold.Alternatively, the add-on assemble can add after shape substrate, and can be by adhesive
It adheres in substrate or can be with thermoforming in the substrate.
Add-on assemble after moulding the substrate and is being added the substrate by embodiment according to the method for the present invention
After upper, then the substrate is introduced into mold.The mold can optionally be for moulding the substrate or applying the add-on assemble
Same mold the second cavity.The mold is opened and the substrate is transferred in cavity.The transfer of the substrate can be with
Pass through any one progress in a variety of methods.The specific example of suitable method includes but is not limited to use revolving platform, turnover panel, cunning
Dynamic chamber and index plate (index plate) shift and wherein the substrate is retained in the similar approach on type core.If should
Substrate is retained in the type core for transfer, the advantage that be that position can also be accurately defined after the transfer.Another party
Face, wherein for example being removed from a cavity by means of operating system by substrate and being placed into the substrate transfer side in another cavity
Method is also suitable.
Embodiment according to the method for the present invention, by coating composition be introduced into containing molding plastic basis material die cavity in
It coats the substrate and can adhere to any add-on assemble thereon.The coating composition used in the methods of the invention includes (i)
Polymer and (ii) polyisocyanates containing isocyanate-reactive group.In certain embodiments, which is
High solids content (solids) composition, as used in this article, high-solids composition mean that the coating composition includes base
It is no more than 10 weight %, preferably more than 2 weight % in the total weight of the composition, particularly no more than 1 weight %'s
Volatile material (such as organic solvent or water).In certain embodiments, the composition is that have opposite low viscosity, hydroxy radical content
It is relatively low viscous as used in this article for the 100% solid content composition of 15.4-16.6% (being measured according to DIN 53 240/2)
It is (viscous using rotation when being measured according to DIN EN ISO 3219/A3 that degree refers to that the viscosity at 23 DEG C is no more than 12,000mPas
Spend meter-Visco550, Thermo Haake GmbH measurement).
Suitably the polymer containing isocyanate-reactive group includes such as polymer polyatomic alcohol, such as polyether polyols
Alcohol, polyester polyol and/or polycarbonate polyol etc..
Suitable polyether polyol includes but is not limited to MnIt is those of 100 to 4,000g/mol.Sometimes it uses by repeating
Ethylene oxide and propylene oxide units formed polyether polyol, such as with 35% to 100% propylene oxide units (such as
Those of 50% to 100% propylene oxide units) content.These can be the random copolymerization of ethylene oxide and propylene oxide
Object, gradient copolymer or alternating or block copolymer.Suitably it is derived from duplicate propylene oxide and/or ethylene oxide unit
Polyether polyol be commercially available, and including for example can from such as Covestro LLC, Pittsburgh,
Those of Pennsylvania acquisition (such as3600Z、1900U、Polyol
2200、Polyol 40001、Polyol 1004、Polyol 1010、Polyol
1030、Polyol 1070、BD 1110、VPPU 0789、K55、
1004、S180)。
In certain embodiments of the invention, the polymer polyatomic alcohol includes polyester polyol, such as MnIt is 200 to 4,
Those of 500g/mol.In certain embodiments, viscosity of the polyester polyol at 23 DEG C is 700 to 50,
000mPas and hydroxyl value are 200 to 800mgKOH/g.In certain embodiments, the polyester polyol is based on aromatics carboxylic
Acid polyester, average hydroxy functionality is greater than 2 (preferably 3 or bigger), average hydroxyl value be 350 to 700mgKOH/g (such as 450 to
Viscosity 600mgKOH/g) and at 23 DEG C is 1000 to 30000mPas.As it will be appreciated, suitable polyester polyol
It can be by making polybasic carboxylic acid, carboxylic acid anhydrides, lactone or the C of polyalcohol and stoichiometric amount1-C4The polycarboxylate of alcohol reacts to make
It is standby.
In certain embodiments, the polyester polyol is derived from one or more of aromatic polycarboxylic acids or its acid
Acid anhydride, ester derivant, 6-caprolactone are (optionally in the mixing with one or more of aliphatic series or alicyclic polycarboxylic acid or derivatives thereof
Object form).
Suitable number-average molecular weight be 118 to 300g/mol and the compound of average carboxyl functionality > 2 (it is suitable for systems
Standby polyester polyol) it include but is not limited to adipic acid, phthalic anhydride and M-phthalic acid, or use its mixture.
In order to prepare polyester polyol, suitable polyalcohol has the number of 62-400g/mol in some embodiments
Those of average molecular weight, such as 1,2- ethylene glycol, 1,2- and 1,3-PD, the butanediol of isomery, pentanediol, hexylene glycol, heptan two
Pure and mild ethohexadiol, 1,2- and Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, 4,4 '-(1- methyl ethylidene)-biscyclohexanols,
Glycerin, 1,1,1- trimethylolethane, 1,2,6- hexanetriols, 1,1,1- trimethylolpropane, 2,2- (bis- (hydroxyl first
Base) -1,3-PD.In certain embodiments, the polyalcohol include 1,2-PD, 1,3-BDO, 1,6- hexylene glycol,
Neopentyl glycol and/or trimethylolpropane, such as 1,3-BDO, neopentyl glycol and/or trimethylolpropane.In certain embodiment party
In case, polyester polyol include branched polyesters polyalcohol, the example be can from Covestro LLC, Pittsburgh,
What Pennsylvania was obtainedXP 2488。
In certain embodiments of the invention, polymer polyatomic alcohol includes aliphatic polycarbonate polyalcohol, such as poly- carbonic acid
Esterdiol, such as MnIt is 200 to 5000g/mol (such as 150 to 4,500g/mol, 300 to 2000g/mol, 300 to 2,500g/mol
Or 400 to 1000g/mol) and hydroxy functionality be those of 1.5 to 5 (such as 1.7 to 3 or 1.9 to 2.5).In certain embodiment party
In case this kind of polycarbonate polyol can also the viscosity at 23 DEG C be 2000 to 30,000mPas, preferably 2500 to
16000mPas, most preferably 3000 to 5000mPas (use rotary viscosity when measuring according to DIN EN ISO 3219/A3
Meter-Visco550, Thermo Haake GmbH measurement), hydroxy radical content is 15.4-16.6% (according to DIN
53240/2 measures) and/or hydroxyl value be 40 to 300mgKOH/g (such as 50 to 200mgKOH/g or 100 to 200mgKOH/g) (when logical
When crossing end-group analysis well known in the art and measuring).
This kind of aliphatic polycarbonate polyalcohol can for example pass through monomer dialkyl carbonate such as dimethyl carbonate, carbonic acid two
Polyalcohol such as 1,4-butanediol, 1,3-BDO, 1,5- of ethyl ester or diphenyl carbonate and the hydroxy functionality at least 2.0
Pentanediol, 1,6- hexylene glycol, 3- methyl-1,5- pentanediol, 1,12- dodecanediol, cyclohexanedimethanol, trimethylolpropane
And/or it is any these mixture and the ester exchange reaction of lactone such as 6-caprolactone prepare.In certain embodiment party of the invention
In case, aliphatic polycarbonate polyalcohol is by 1,4-butanediol, 1,6- hexylene glycol, 3- methyl-1,5- pentanediol or its two kinds or more
A variety of mixtures is prepared with 6-caprolactone.For example, Covestro LLC, Pittsburgh are come from, Pennsylvania'sC type is such asC 1100 or Desmophen C 2200 may be used as polycarbonate glycol.
In certain embodiments of the invention, the polymer containing isocyanate-reactive group includes: (i) polyester
Polyalcohol, such as branched polyesters polyalcohol, and (ii) polycarbonate polyol, such as polycarbonate glycol, such as polycarbonate polyester two
Alcohol, such as based on those of 1,6- hexylene glycol and 6-caprolactone.In certain embodiments, coating group used in the method for the present invention
The weight ratio of (i) and (ii) in object is closed in 1: 10 to 10: 1 (such as 1: 5 to 5: 1,1: 4 to 4: 1,1: 3 to 3: 1,1: 2 to 2: 1) model
It is 1: 1 in enclosing or in some cases.In certain embodiments, the polymer containing isocyanate-reactive group is selected
(or mixture of two or more this as described above quasi polymers) so as at 23 DEG C with relatively low viscosity (according to
DIN EN ISO 3219/A.3 is measured), preferably more than 10,000mPas, most preferably not more than 8,000mPas.
It as mentioned, also include polyisocyanates for the coating composition of the method for the present invention.Suitable polyisocyanates
Including aromatics, araliphatic, aliphatic series or alicyclic two-and/or polyisocyanates and its mixture.In certain embodiments, institute
Stating polyisocyanates includes formula R (NCO)2Diisocyanate, wherein R represent have 4 to 12 carbon atoms aliphatic hydrocarbon residue,
Clicyclic hydrocarbon residue with 6 to 15 carbon atoms, the aromatic hydrocarbon residues with 6 to 15 carbon atoms have 7 to 15 carbon
The araliphatic hydrocarbon residue of atom.The specific example of suitable diisocyanate includes benzene dimethylene diisocyanate, four methylenes
Group diisocyanate, Isosorbide-5-Nitrae-diisocyanate root close butane, 1,12- diisocyanate root is puted the palms together before one dioxane, hexamethylene diisocyanate,
2,3,3- trimethyl hexamethylene diisocyanates, Isosorbide-5-Nitrae-cyclohexylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride, two isocyanide
Acid esters, 4,4 '-dicyclohexyl diisocyanate, 1- diisocyanate root close -3,3,5- trimethyl -5- isocyanatomethyl hexamethylenes
Alkane-(isophorone diisocyanate), Isosorbide-5-Nitrae-phenylene diisocyanate, 2,6- toluene di-isocyanate(TDI), 2,4- toluene diisocynate
Ester, 1,5- naphthalene diisocyanate, 2,4 '-or 4,4 '-methyl diphenylene diisocyanates, 4,4 '-diphenyldimethyhnethanes two
Isocyanates, α, α, α ', α '-tetramethyl-is m- or-p- benzene dimethylene diisocyanate and triphenyl methane 4,4 ', 4 "-three
Isocyanates and its mixture.Equally suitable is monomer triisocyanate such as eight methylene of 4- isocyanatomethyl -1,8-
Group diisocyanate.
Contain isocyanuric acid ester, imino group oxadiazines diketone, carbamate, biuret, allophanate, urea diketone
And/or the polyisocyanate adduct of carbodiimide group is also applied for coating composition used in the method for the present invention.It is such
Polyisocyanates can have 3 or bigger isocyanate functionality, and can be for example by the trimerization of diisocyanate or low
It is poly- or prepared by reacting for diisocyanate and the polyfunctional compound containing hydroxyl or amine groups.It is special real at one
It applies in scheme, the polyisocyanates is the isocyanuric acid ester of hexamethylene diisocyanate, can be according to U.S. Patent number
The 5th row of 4,324,879 the 3rd column is prepared to the 47th row of the 6th column, and reference portion is incorporated herein by reference.
In certain embodiments of the invention, the coating composition includes low viscosity polyisocyanates, the low viscosity
Viscosity of the polyisocyanates at 23 DEG C and under 100% solid content be less than 2000mPas (such as less than 1500mPas or
800 to 1400mPas under some cases) (rotational viscometer-Visco is used when measuring according to DIN EN ISO 3219/A3550, Thermo Haake GmbH measurement)；Isocyanate content is 8.0 to 27.0 weight % (such as 14.0-
24.0 weight % or 22.5-23.5%) (according to DIN EN ISO 11909)；It is 2.0 to 6.0 (such as 2.3 that NCO, which calculates degree of functionality,
To 5.0 or 2.8 to 3.2)；And monomeric diisocyanate content is less than 1 weight % (such as less than 0.5 weight %).
The example of these polyisocyanates includes by making hexamethylene diisocyanate trimerization until the reaction mixture
With 42 weight % to 45 weight %, (NCO content of such as 42.5 weight % to 44.5 weight %) then terminates the reaction and leads to
Cross the urea containing isocyanide that distillation removes the residual content of unreacted hexamethylene diisocyanate to less than 0.5 weight % to prepare
The polyisocyanates of acid esters group；What can be mixed with the polyisocyanates containing isocyanurate group contains uretdion groups
Polyisocyanates；It can be disclosed according in U.S. Patent number 3,124,605,3,358,010,3,903,126 and 3,903,127
Method preparation biuret-containing group polyisocyanates；It can be according to U.S. Patent number 5,124,427,5,208,334 and
The polyisocyanates containing isocyanuric acid ester and allophanate groups of the preparation of method described in 5,235,018；And it can be with
The imido- oxadiazines diketone for preparing as described in DE-A 19611849 in specifically in the presence of containing fluorine catalyst and optionally different
The polyisocyanates of isocyanurate groups.
It can be usefully using cyclic annular and/or linear polyisocyanates molecule.It is different in order to improve weatherability and reduce yellow
The polyisocyanates of isocyanate component is usually aliphatic series.
In certain embodiments of the invention, the polyisocyanates is comprising following components or basic in some cases
Be made from it or be made from it: the polyisocyanates of biuret-containing group (such as can be with trade nameN-100 from
Covestro LLC obtain hexamethylene diisocyanate (HDI) biuret adduct), containing the more of isocyanurate group
Isocyanates (such as can be with trade nameThe polyisocyanates that N-3300 is obtained from Covestro LLC) and/or contain
The polyisocyanates of carbamate groups, uretdion groups, carbodiimide group, allophanate groups etc..These spread out
Biology is to show low-down vapour pressure, and substantially free of isocyanates preferably as they are polymer-types
Monomer.
The polyisocyanates is generated with the pre-reaction of material containing hydroxy groups with higher compared with individual polyisocyanates
Molecular weight and lower isocyanate content modified polyisocyanate.This usually will lead to viscous in modified polyisocyanate
Du Genggao.Usually desirably, the viscosity of modified polyisocyanate is low, for example, wherein 25 DEG C to 70 DEG C at a temperature of
Brookfield viscosity be less than about 10,000mPas (such as less than 5,000mPas or in some cases less than 4,
Those of 000mPas).Illustrative such polyisocyanates includes can be with trade nameN-3600 from
Covestro LLC is those of commercially available, and the viscosity at 25 DEG C is 800-1400mPas.
During forming the coating composition for being used for the method for the present invention, the polymer containing isocyanate-reactive group
(polyalcohol as mentioned earlier) and polyisocyanates are so that the coating composition has 0.8 to 3.0: 1 (such as 0.8 to 2.0: 1
Or in some cases 1: 1 to 1.8: 1 or 1: 1 to 1.5: 1) ratio of isocyanate groups and isocyanate-reactive group
Relative quantity combination.In some embodiments, which is greater than 1: 2: 1, such as at least 1: 3: 1 and/or highest 1: 4: 1.It is true
On, it is now recognized that this " the super indexation (over-indexing) " of isocyanate groups and isocyanate-reactive group can
Can substrate to the molding after curing of coating composition through coating only demoulded from the second die cavity via gravity or only with suction
Ability has notable contribution, because, under the conditions of the temperature of the raising used in the methods of the invention and the pressure-cure of raising, institute
Have or essentially all of isocyanate-reactive group (such as hydroxyl group) is considered solidifying and being exposed to moisture or shape
At allophanate groups, the more complete solidification of coating composition is thus provided.
Coating composition for the method for the present invention is further included for isocyanate-reactive group (such as hydroxyl base
Group) with the catalyst reacted between isocyanate groups.Suitable such catalyst includes metal and non-metallic catalyst,
Specific example includes but is not limited to amine catalyst, such as 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene (DBU), Isosorbide-5-Nitrae-phenodiazine
Miscellaneous bicyclic [2.2.2] octane (DABCO) or triethanolamine and lewis acid compound, such as dibutyl tin dilaurate, octanoic acid
Lead, tin octoate, titanium and the complex of zirconium, cadmium compound, bismuth compound such as bismuth neodecanoate and iron compound.In certain implementations
In scheme, catalyst is present in coating composition by the amount for being no more than 1.0 weight % based on the total solid content of composition.
Coating composition for the method for the present invention can further include plasticizer, for reducing the viscous of composition
Degree.It explains in detail as follows, the viscosity of the coating composition at processing temperatures is preferably (200-500 lis of 200-500mPas
Pool), and the processing temperature be 50-120 DEG C (120-248 °F), preferably 50-80 DEG C (120-177 °F), most preferably 66-77
℃(150-170°F).In order to reach this relatively low levels of viscosity, it may be necessary to which addition has been found that reducing composition glues
The plasticizer of degree.The plasticizer is preferably free of phthalic acid ester, such as the ester of alkyl sulfonic acid and phenol, by
LANXESS Deutschland GmbH, Leverkusen, Germany is with trade mark Mesamoll sale.
Coating composition of the invention may include silicone, can serve as internal mold release in the coating composition, thus
Cured coating is promoted only to pass through gravity or be only detached from from die cavity with suction when the mold is open.The silicone can be polyethers and change
Property silicone compounds, the substrate for such as tending to increase coated molding when the mold is open can be only by gravity or only with inhaling
The such compound for a possibility that power is detached from from die cavity.
The example for being suitable for the invention polyether-modified silicone includes wherein at the end of polysiloxanes and/or side chain
Compound comprising polyether chain, and further include wherein in polysiloxanes also comprising the common modified silication of different organic groups
Close object.Furthermore it is possible that polyether-modified silicone includes (methyl) acryl group in the molecule.
The example for being suitable for the invention polyether-modified silicone compounds includes but is not limited toSilicone, such as but
It is not limited toIt is the solvent-free polyether-modified hydroxyl-functional polydimethylsiloxanes from BYK USA Inc.
Alkane.
The example for being suitable for the invention other internal mold releases includes wherein at the end of polysiloxanes and/or side chain
The silicone compounds of polyester modification comprising polyester chain, and further include wherein in polysiloxanes also together comprising different organic
The common modified silicon compound of group.Furthermore it is possible that the silicone of polyester modification includes (methyl) acryloyl group base in the molecule
Group.
The example for being suitable for the invention the silicone compounds of polyester modification includes but is not limited toSilicone, such as but
Be not limited to BYK-370, be the polyester modification from BYK USA Inc. hydroxy-functional polydimethylsiloxanes dimethylbenzene,
75% solids solution in alkylbenzene, cyclohexanone and single phenyl glycol.
In certain embodiments of the coating composition for the method for the present invention, internal mold release (such as aforementioned silicone) with
(amount of such as 0.1 weight % to 1.0 weight %) are present in 0.1 weight % of total weight to 5 weight % based on coating composition
In the composition.In certain embodiments of the invention, internal mold release is surveyed with being enough to provide to have when using Ram é-Hart
Instrument measurement in angle (wherein calculates total solid surface energy, including polar component and dispersion using advancing angle according to Owens Wendt program
Component, and wherein sample is stacked in the case where not having surface protection, and the surface is slightly wiped before analysis
Wipe with except dust) when be no more than 30 dynes per centimeters (as being no more than 25 dynes per centimeters) surface tension solidify coating amount
It is present in the composition.
Coating composition for the method for the present invention may include any conven-tional adjuvants and additive of technical field of coatings,
Such as defoaming agent, thickener, pigment, dispersing aid, catalyst, anti skinning agent, sagging inhibitor or emulsifier, as example.
As previously mentioned, in the methods of the invention, by coating composition be introduced into the die cavity of the plastic basis material containing molding with
The substrate is coated, and solidifies the composition in die cavity under the pressure of raising and the condition of cure of temperature.If using double
Those of component coating composition, especially because there is short Storage period there are the curing catalysts of sufficient amount, these components
It can be mixed in injection nozzle (such as high pressure adverse current mixing head) or in the feed line by static mixer or by means of dynamic
Active mixing (depending on Storage period and equipment and technology) Lai Jinhang of clutch is sufficiently mixed.If since for example there is no any
If curing catalysts or the curing catalysts of sufficiently low amount and Storage period are long, the mixing of two kinds of components can also be in equipment
(installation) external to carry out, and mixture can be handled as single-component system.In this case, for example,
Can be extended by cooling down the component before the injection processing the time, and can by improve the mold temperature in the cavity come
Realize short reaction time.
In embodiments of the invention, coating step carries out under stress.This means that being applied to the plastic basis material of molding
Coating composition is added to carry out under stress.In certain embodiments, by the way that coating composition is injected into substrate under stress
Apply coating in gap between surface and cavity inner wall.The pressure is sufficiently high for cavity, passes through external pressure
Device such as fixture (described in greater detail below) pressurizes, and fills before terminating so as to the Storage period in coating composition.
Meanwhile pressure prevents from forming bubble in the flow front of coating composition.
The solidification of coating composition also carries out under stress.In the context of the present invention, the solidification meaning of coating composition
Taste the coating it is cured to sufficient degree so that once opening mold, the substrate of coated molding is when mold is opened
Only pass through gravity or be only detached from from the mold with suction, that is, demoulds.At the end of curing time, the pressure in the cavity may
Have been lowered to environmental pressure.
Several factors help to carry out the ability of in-mould coating method, wherein die cavity is once opened, coated molding
Plastic basis material only passes through gravity when the mold is opened or is at most only detached from suction from the inner surface of the second mold, i.e., de-
Mould removes the substrate of coated molding without any additional power or effort from cavity.Particularly, mold temperature
Degree, outer mold pressure, the composition (presence including internal mold release as described above and preceding of curing time, coating itself
The ratio of isocyanate groups described in face and isocyanate-reactive group) and external release agent described below presence
Combination respectively can and the mold cured in coating composition to coated molded substrate be opened after only via weight
Power only has significant contribution with the ability that suction is demoulded from the second die cavity.
More particularly, selection coating composition (presence including internal mold release as described above and mentioned-above different
The ratio of cyanate group and isocyanate-reactive group) and curing time used, mold temperature and outer mold pressure
Selected combination so that the urea groups of the polyurethane chain in solidify coating are cross-linked to each other in the coating, thus improve polyurethane polyureas
The crosslink density of polymeric network.Think to survey when opening mold by the content for the urea groups that dissociate in analysis solidify coating
This crosslinking of weight polyurethane chain.
Coating composition is injected into die cavity.The die cavity can have any required design, so that if desired, applying
Bed of material thickness having the same in the whole surface of substrate, also referred to as " conformal coating ".In other cases, if it is desired,
Cavity can be made to be shaped so that dope layer has different thickness in each region of substrate, so that when it encapsulates sensitivity
There is with a kind of thickness when add-on assemble when it only covers substrate another thickness.For example, mold cavities shaped can be made
(or even including the position of add-on assemble in substrate) provides substantially smooth surface at away from substrate constant distance.This is also referred to as
" non-conformal coating ".Essentially smooth surface appears in the ground that the distance between substrate and coating surface are in essentially constant distance
Side, deviation are 10% or smaller, and preferably deviation is 5% or smaller.In some cases, die cavity can have grain surface or can
With attempting to include required design or mark in the coating.Needed for being realized in this way in any position of substrate
Thickness of coating layer.In certain embodiments of the invention, external release agent is present on the surface of one or both of cavity.
Particularly, the coating comprising chemical plating (electroless) nickel and polytetrafluoroethylene (PTFE) (PTFE) is suitable as external release agent.This
Class coating can be from Poly-Plating, and Inc. is with trade nameIt is commercially available.In certain embodiments of the present invention
In, it at the thickness of dry film of dope layer caused by making is 0.05 to 3.5 millimeter, preferably 0.5 to 3.0 millimeter by cavity design.
By coating composition be injected into die cavity can by by composition via one or more nozzle injections to mould
It is completed in chamber, so that the gap between the surface and mould inner wall of the substrate of molding is filled up completely by coating composition.For
The coating composition is most preferably injected, can properly select the quantity of injection point in the manner known to persons skilled in the art
The position and.Die cavity can be designed to the controlled displacements of air present in offer cavity, and via parting line during injection
Or venting channels remove the air.Known calculation procedure can be used thus.For injecting the cast gate of the coating composition
Design can be for example according to well known in the prior art for producing the cast gate variant of RIM mechanograph.
In certain embodiments, it is coated by RIM method with single cavity.This has the double of the coating composition
The advantages of two kinds of components in component only just combined in being injected into cavity not long ago.In certain embodiments, this pass through by
The component (as described above) of the resin containing isocyanate-reactive and component (as described above) comprising polyisocyanates are from RIM equipment
It is fed in impact type mixing head and realizes, wherein the component is mixed before being injected into die cavity.In general, every kind of component
It is fed in impact type mixing head via the aperture that diameter is 0.15mm-0.70mm.
In embodiments of the invention, by mixture with 10-60 Grams Per Second, preferably 15-40 Grams Per Second flow velocity 1600
To 3000psi (11,000 to 20,700kPa), preferably 1800 to 2200psi (12,400 to 15,200kPa) line pressure and
50-120 DEG C (120-248 °F), preferably 50-80 DEG C (120-177 °F), the bet of most preferably 66-77 DEG C (150-170 °F) of temperature
It is mapped in the second die cavity.Although line pressure above may seem high, but it is understood that, in injection coating composition
Later, the fine add-on assemble in die cavity will not face such pressure.Specifically, it is contemplated that the intracorporal pressure of the chamber significantly drops
It is low.The viscosity of the mixture at processing temperatures is preferably 200-500mPas (200-500cP).The mixture compared with
Low viscosity is combined with higher injection temperature, reduces the power being applied on add-on assemble, and ensures the mixture shape simultaneously
At the expection coating of add-on assemble or encapsulation.
Once coating composition, in the die cavity, it is exposed to the condition of cure of the temperature improved and outer mold pressure
Under.
It is such as 62 DEG C to 105 DEG C, preferably 71 DEG C to 82 DEG C (160-180 ° for proper mold temperature range of the invention
F).As used herein, " outer mold pressure " refer to when firmly make the opposite face of mold together when be applied to mold (its
In be equipped with cavity) opposite face on from outside apply pressure.The source of this pressure can be fixture, plunger or other dresses
It sets.These embodiments it is certain in, outer mold pressure is at least 100kg/mm2(9807 bars), for example, at least 110kg/
mm2(10787 bars), or at least 120kg/mm2(11768 bars).In in these embodiments certain, outer mold pressure is not
More than 200kg/mm2(19613 bars), such as no more than 180 (17652 bars) or it is no more than 160kg/mm2(15691 bars).Certain
In embodiment, outer mold pressure keeps relative constant during curing of coatings.In certain embodiments, it reacts (i.e.
Solidification) time is at least 60 seconds, for example, at least 70 seconds.These embodiments it is some in, curing time be no more than be 120
Second.
As it will be appreciated, can also be carried out in the mold with more than two cavity according to the method for the present invention.Therefore,
Such as add-on assemble can apply in another cavity.It is also possible to apply other dope layers with optional particular characteristic,
This is carried out by adding each dope layer in its respective cavity.Furthermore, it is possible in a cavity one concurrently manufacture
The plastic basis material of multiple moldings, then in a cavity successively or in a cavity one concurrently these are coated.
The Coinjection molding apparatus of mold according to the present invention is used in the first cavity of mold by injection moulding by heat
Plasticity or thermosetting plastics manufacture substrate.Suitable Coinjection molding apparatus is known to the skilled in the art.They include mark
Quasi- injection (mo(u)lding) machine construction comprising the traveling of plasticization unit and responsible mold for substrate processing, opening and closing fortune
Dynamic closed cell, temperature control device and optional substrate drier.
The coating injection device for the second cavity being connected in mold according to the present invention is for coating substrate.It is suitable to apply
Material injection device may include it is one or more for the storage container of each component, blender, feed pump, for establishing temperature
Temperature control equipment, feeding line and optional for mixing the mixing arrangement of more than one coating composition, such as height
Pressure regurgitates the mixing head of mixing.
The plastic basis material of the coated molding manufactured by the method for the invention is applicable to coat or encapsulate finely
The various applications of add-on assemble, otherwise these add-on assembles may be damaged due to following prior art cladding process.
In addition, following aspect of the invention is listed as follows:
1. the method for being used for in-mould coating comprising: (a) plastic basis material is introduced into the membrane cavity of mold；(b) (i) is in processing temperature
At 50 DEG C -120 DEG C of degree, (ii), which introduces coating composition under tonnage 11,000 to 20,700kPa, contains the plastics
To coat the substrate in the die cavity of substrate；(c) make the composition in the die cavity solid under 62-105 DEG C of solidification temperature
Change；Wherein the coating composition includes polymer and polyisocyanates containing isocyanate-reactive group, and wherein described
Viscosity of the coating composition under the processing temperature is 200 to 500mPas.
2. 1 method, wherein the plastic basis material includes aromatic polycarbonate.
3. the method for any of above-mentioned aspect, wherein at least one of electronic circuit, light emitting diode and graph image are attached
On the plastic basis material.
4. the method for any of above-mentioned aspect, wherein the processing temperature is 50-80 DEG C, preferably 66-77 DEG C.
5. the method for any of above-mentioned aspect, wherein the tonnage is 12,400 to 15,200kPa.
6. the method for any of above-mentioned aspect, wherein the mold temperature is 71 DEG C to 82 DEG C.
7. the method for any of above-mentioned aspect, further comprise by the polymer of the resin containing isocyanate-reactive and
The polyisocyanates is mixed into the step in mixing head, wherein component is mixed before being injected into the die cavity.
8. the method for any of above-mentioned aspect, wherein the polymer and the polyisocyanate cyanogen of the resin containing isocyanate-reactive
One of acid esters is fed in impact type mixing head via the aperture that diameter is 0.15mm-0.70mm.
9. the method for any of above-mentioned aspect, wherein the polymer containing isocyanate-reactive group includes: (i) aromatics
Branched polyester polyalcohol；(ii) aliphatic polycarbonate polyalcohol.
10. the method for any of above-mentioned aspect, wherein the aliphatic polycarbonate polyalcohol is polycarbonate glycol.
11. the method for any of above-mentioned aspect, wherein the polyisocyanates includes the isocyanide of hexamethylene diisocyanate
Urea acid esters.
12. the method for any of above-mentioned aspect, wherein the coating composition with a thickness of 0.05mm to 3.5mm, preferably
0.5mm-3.0mm。
13. the method for any of above-mentioned aspect, wherein coating surface substantially constant at a distance from the substrate.
14. the method for any of above-mentioned aspect, wherein the coating composition also includes plasticizer.
15. the method for any of above-mentioned aspect further comprises molded plastic substrate.
16. the method for any of above-mentioned aspect, wherein the mold includes the first cavity and the second cavity, in first chamber
The plastic basis material is moulded in body and the coating composition is introduced into second cavity.
17. the method for any of above-mentioned aspect further comprises that addition includes electronic circuit, light emitting diode and/or figure
The film of shape image.
18. 17 method, wherein being applied to the film in the cavity for wherein moulding the plastic basis material.
19. the method for any of above-mentioned aspect further comprises by electronic circuit, light emitting diode and/or graph image
It is added on the plastic basis material, then introduces the coating composition.
Claims (19)
1. the method for being used for in-mould coating comprising:
(a) plastic basis material is introduced into the membrane cavity of mold；
(b) (i) at 50 DEG C -120 DEG C of processing temperature,
(ii) under tonnage 11,000 to 20,700kPa
Coating composition is introduced into the die cavity containing the plastic basis material to coat the substrate；With
(c) solidify the composition in the die cavity；
Wherein the coating composition includes polymer and polyisocyanates containing isocyanate-reactive group, and
Wherein viscosity of the coating composition under the processing temperature is 200 to 500mPas.
2. the method for claim 1 wherein the plastic basis material includes aromatic polycarbonate.
3. the method for claim 1 wherein at least one of electronic circuit, light emitting diode and graph image be attached to it is described
On plastic basis material.
4. the method for claim 1 wherein the processing temperature is 50-80 DEG C, preferably 66-77 DEG C.
5. the method for claim 1 wherein the tonnage is 12,400 to 15,200kPa.
6. the method for claim 1 wherein the mold temperature is 71 DEG C to 82 DEG C.
It further comprise by the polymer of the resin containing isocyanate-reactive and described more 7. method of claim 1
Isocyanates is mixed into the step in mixing head, wherein component is mixed before being injected into the die cavity.
8. method for claim 7, wherein the polymer and the polyisocyanates of the resin containing isocyanate-reactive it
One is fed in impact type mixing head via the aperture that diameter is 0.15mm-0.70mm.
9. the method that benefit requires 1, wherein the polymer containing isocyanate-reactive group includes: (i) aromatics branched polyester
Polyalcohol；(ii) aliphatic polycarbonate polyalcohol.
10. method for claim 9, wherein the aliphatic polycarbonate polyalcohol is polycarbonate glycol.
11. the method for claim 1 wherein the polyisocyanates includes the isocyanuric acid ester of hexamethylene diisocyanate.
12. the method for claim 1 wherein the coating compositions with a thickness of 0.05mm to 3.5mm, preferably 0.5mm-
3.0mm。
13. the method for claim 1 wherein coating surfaces at a distance from substrate substantially constant.
14. the method for claim 1 wherein the coating composition also includes plasticizer.
15. method of claim 1 further comprises molded plastic substrate.
16. the method for claim 11, wherein the mold includes the first cavity and the second cavity, the mould in first cavity
It makes the plastic basis material and the coating composition is introduced into second cavity.
17. method of claim 1 further comprises that addition includes electronic circuit, light emitting diode and/or graph image
Film.
18. the method for claim 1 wherein the film is applied in the cavity for wherein moulding the plastic basis material.
19. method of claim 1 further comprises that electronic circuit, light emitting diode and/or graph image are added to institute
It states on plastic basis material, then introduces the coating composition.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2017/026588 WO2018186886A1 (en) | 2017-04-07 | 2017-04-07 | Processes for in-mold coating of polymer substrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110494465A true CN110494465A (en) | 2019-11-22 |
Family
ID=58579312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780089411.4A Pending CN110494465A (en) | 2017-04-07 | 2017-04-07 | Method for in-mould coating polymeric substrate |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20200061875A1 (en) |
| EP (1) | EP3606977A1 (en) |
| KR (1) | KR102363743B1 (en) |
| CN (1) | CN110494465A (en) |
| WO (1) | WO2018186886A1 (en) |
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| JP2020183456A (en) * | 2019-04-26 | 2020-11-12 | 日本ペイント・オートモーティブコーティングス株式会社 | Two-part coating composition |
| JP6949291B1 (en) * | 2020-04-10 | 2021-10-13 | 関西ペイント株式会社 | Paint composition and mold inner coating method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016028568A1 (en) * | 2014-08-22 | 2016-02-25 | Covestro Llc | Processes for in-mold coating using a multi-cavity mold and substrates coated thereby |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124605A (en) | 1963-12-05 | 1964-03-10 | Biuret polyisocyanates | |
| US3358010A (en) | 1964-03-11 | 1967-12-12 | Mobay Chemical Corp | Biuret polyisocyanates |
| DE2308015B2 (en) | 1973-02-17 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Process for the production of polyisocyanates with a biuret structure |
| US3903126A (en) | 1973-12-11 | 1975-09-02 | Basf Ag | Manufacture of biuret group-containing polyisocyanates |
| CA1112243A (en) | 1978-09-08 | 1981-11-10 | Manfred Bock | Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof |
| US5124427A (en) | 1991-01-22 | 1992-06-23 | Miles Inc. | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions |
| US5235018A (en) | 1991-07-22 | 1993-08-10 | Miles Inc. | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions |
| US5208334A (en) | 1991-07-22 | 1993-05-04 | Miles Inc. | Process for the production of polyisocyanates containing allophanate and isocyanurate groups |
| DE19611849A1 (en) | 1996-03-26 | 1997-10-02 | Bayer Ag | New isocyanate trimer and isocyanate trimer mixtures, their production and use |
| US20090239043A1 (en) * | 2008-03-24 | 2009-09-24 | Ppg Industries Ohio, Inc. | Oleophilic compositions, coatings employing the same, and devices formed therefrom |
| JP5594037B2 (en) * | 2009-10-23 | 2014-09-24 | Ｊｎｃ株式会社 | Curable resin composition and optical film |
-
2017
- 2017-04-07 CN CN201780089411.4A patent/CN110494465A/en active Pending
- 2017-04-07 WO PCT/US2017/026588 patent/WO2018186886A1/en active Application Filing
- 2017-04-07 EP EP17718693.9A patent/EP3606977A1/en active Pending
- 2017-04-07 US US16/500,505 patent/US20200061875A1/en not_active Abandoned
- 2017-04-07 KR KR1020197028643A patent/KR102363743B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016028568A1 (en) * | 2014-08-22 | 2016-02-25 | Covestro Llc | Processes for in-mold coating using a multi-cavity mold and substrates coated thereby |
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| KR20190133685A (en) | 2019-12-03 |
| KR102363743B1 (en) | 2022-02-15 |
| EP3606977A1 (en) | 2020-02-12 |
| US20200061875A1 (en) | 2020-02-27 |
| WO2018186886A1 (en) | 2018-10-11 |
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